Determination of Trace Elements in Vegetable Oils and Biodiesel by Atomic Spectrometric Techniques—A Review

Abstract

The determination of trace elements in edible oils and biodiesel using atomic spectrometric methods is reviewed. Problems related to sample pretreatment for appropriate sample introduction and calibration are addressed as well as the strategies to overcome them. Recent trends aimed at simplifying sample manipulation are presented. The applications and scope of atomic absorption spectrometry (AAS), flame optical emission spectrometry (F-OES), inductively coupled plasma–optical emission spectrometry (ICP-OES), and inductively coupled plasma–mass spectrometry (ICP-MS) techniques for the determination of trace metals in edible oils and biodiesel are discussed, as well as some current instrumental new developments.     

Current Status of Direct Solid Sampling for Electrothermal Atomic Absorption Spectrometry—A Critical Review of the Development between 1995 and 2005

Abstract

The literature about direct solid sampling (SS) and slurry sampling atomic absorption spectrometry (AAS) over the past decade has been surveyed critically. It became apparent that a very significant change had occurred, particularly in the relation between the two major techniques used for that purpose. In the 1990s, slurry sampling was typically considered the technique of choice, combining the significant advantages of the solid and the liquid sampling methods, at least in part because of the availability of a commercial accessory for automatic slurry sampling. The situation is completely inverted now, as the above accessory has been discontinued and rugged and reliable accessories for direct SS became available. Direct SS electrothermal (ET) AAS has been shown to provide the best limits of detection because of the absence of any dilution and a minimal risk of contamination. Calibration against aqueous standards appears to be feasible after careful program optimization. The absence of any significant sample handling makes SS ET AAS ideally suited for fast screening analyses. The introduction of high‐resolution continuum source AAS appears to open additional attractive features for SS ET AAS because of the significantly simplified optimization of furnace programs and the visibility of the spectral environment, which makes it easy to avoid spectral interferences. New calibration strategies make a “dilution” of samples unnecessary, which used to be one of the major limitations of SS ET AAS. Finally, direct SS analysis is an important contribution to clean chemistry, as practically no reagents are used.     

Recent Developments in Ion Mobility Spectrometry

Abstract

The general principles and technical implementations of traditional time-of-flight ion mobility spectrometers and analyzers with field-dependent mobilities were reviewed in our last article in this journal. Recent advances in instrumentation and new applications since 2006 are highlighted in this review. In addition to traditional applications as military chemical-agent detectors, ion mobility techniques have become popular for different purposes. Though ion mobility spectrometry was solely used as vapor sensor in the past decades, further developments in ionization techniques (especially electrospray ionization) now permit its routine use for the analysis of liquid samples. The coupling of ion mobility spectrometry with selective sample preparation techniques such as molecular-imprinted polymers, coupling with chromatographic techniques, the use of dopants, and application of selective ionization sources has led to an expanded number of applications in industrial and environmental analysis with complex sample matrices due to an improved selectivity in comparison with traditional stand-alone spectrometers. Furthermore, new developments in hyphenated techniques, especially ion mobility–mass spectrometry couplings, has resulted in an increased number of new applications for the analysis of biomolecules and pharmaceutical samples and in clinical diagnostics.     

Improved Performance of On-line Atom Trapping in Flame Furnace Atomic Absorption Spectrometry by Chemical Vapor Generation: Determination of Cadmium in High-Salinity Water Samples

ABSTRACT

On-line atom trapping inside a nickel flame furnace using chemical vapor generation for sample introduction was proposed for the determination of trace cadmium by flame atomic absorption spectrometry (AAS). Cadmium volatile species was generated upon reaction with potassium borohydride and then flushed into a flame furnace for on-line trapping by a flow of nitrogen carrier gas. The middle part of the flame furnace, where the carrier gas impacts, is cooled by the gas flow, and this provides a fine strategy for on-line atom trapping for the purpose of preconcentration. A stainless steel plate is put on the top of the flame burner in the middle to form a flame-free zone, which also greatly lowers the temperature of the flame furnace and facilitates the atom-trapping process. Due to the introduction of chemical vapor generation, matrix effect was greatly alleviated compared with direct pneumatic nebulization for on-line atom trapping in flame furnace AAS. With trapping time of 35 s, the current approach achieved an excellent limit of detection of 20 ng L^?1. The proposed method was successfully applied for the quantification of cadmium in high-salinity samples.     

Molybdenum,Platinum, and Tantalum Metal Atomizers or Vaporizers in Analytical Atomic Spectrometry

Abstract

The application of metal (tantalum, molybdenum, and platinum) devices in analytical atomic spectrometry is reviewed in this article. These metal devices have been employed in various analytical atomic spectrometric techniques for more than three decades, mainly as electrothermal atomizers or electrothermal vaporizers, in various physical shapes, such as tubes, platforms, loops, and wires (or coils/filaments). Their application spans from atomic absorption spectrometry (AAS), atomic emission spectrometry (AES) atomic fluorescence spectrometry (AFS), inductively coupled plasma atomic emission spectrometry (ICP‐AES) to inductively coupled plasma mass spectrometry (ICP‐MS). The analytical figures of merit and the practical applications reported for these metal devices are reviewed, and the atomization mechanism on these metal atomizers is briefly summarized, too. In addition, other applications of the metal devices are discussed, including analyte preconcentration by electrodeposition and sequential metal vapor elution analysis (SMVEA). Furthermore, the application of these metals in graphite furnaces encompasses the schemes with the metals in the form of furnace linings, platforms, or impregnated salts.     

Interfacing Microfluidic Handling with Spectroscopic Detection for Real‐Life Applications via the Lab‐on‐Valve Platform: A Review

Abstract

One of the current needs within the analytical spectrometric community is the development of straightforward and cost‐effective, yet rugged, sample processing procedures aimed at precluding both spectroscopic and nonspectroscopic matrix interferences while fostering concomitant sample enrichment. Illustrated via selected representative examples, this review presents and discusses the current state of the art in implementing miniaturised and automated sample treatments for environmental and biochemical assays via microfluidic systems exploiting the lab‐on‐valve (LOV) platform in hyphenation with syringe pump propelling devices as a front end to a plethora of spectroscopic detection schemes including ultraviolet‐visible (UV‐Vis) spectrometry, spectrofluorimetry, chemiluminescence, atomic absorption spectrometry (AAS), atomic flourescence spectrometry (AFS), and inductively coupled plasma‐atomic emission spectrometry/mass spectrometry (ICP‐AES/MS). In contrast to lab‐on‐a‐chip units, the versatile configuration of the micromachined LOV readily facilitates the implementation of on‐line unit operations at will encompassing not merely the introduction of minute, well‐defined volumes of sample followed by chemical derivatization, but the potential for accommodation of solid‐phase extraction, hydride/vapor generation, precipitation/coprecipitation, and bead injection protocols with no need for chip redesign.     

Determination of Selenium (IV) in Natural Waters by HG‐AAS Using an Integrated Reaction Chamber Gas–Liquid Separator

Abstract

A simple online sequential insertion manifold coupled to a hydride generation atomic absorption spectrometer (HG‐AAS) has been developed for selective inorganic Se(IV) determination. The online method is based on the sequential insertion of sample and reagents in the integrated reaction chamber gas–liquid separator (RC‐GLS), which operates initially as reaction chamber for various sample volumes (up to 20 mL) and subsequently as gas–liquid separator with limited dead volume. The generated hydride from a large sample volume is trapped in the RC‐GLS for a short time and then it is flashed in the atomic absorption cell. The HCl and the NaBH₄ concentration was optimized for selective inorganic Se(IV) determination. For 8‐mL and 16‐mL sample consumption, the sampling frequency is 40 h^?1 and 24 h^?1, while the detection limit is 0.04 µg L^?1 and 0.03 µg L^?1, respectively. The precision (relative standard deviation) for 2.0 µg L^?1 Se(IV) (n=10) is 2.6% and 2.8% for 8 mL and 16 mL sample volumes, respectively. The accuracy of the proposed method was evaluated by analyzing the certified reference material, NIST CRM 1643d, and also by analyzing spiked natural water.     

原子吸收光谱法测定中成药阿胶中铜、铬、镉、铅、砷、锑、锡和汞

本文以５０ｍｌ比色管作消化容器，硝酸－高氯酸混酸消化中成药阿胶，采用火焰原子吸收法测定其中的铜；石墨炉法测定其中的铬、镉、铅；氢化物法测定其中的砷、锑、锡。以硝酸－硫酸加过氧化氢水浴加热消化处理样品、采用冷原子法测定其中的汞，均取得较满意的结果。     

Multielement Analytical Spectroscopy in Plant Ionomics Research

Abstract: The study of the ionome (ionomics) is defined as quantitative and simultaneous measurement of the element composition of living organisms and changes in this composition in response to physiological stimuli, development stage, and genetic modifications (Salt et al., Ann. Rev. Plant Biol., Vol. 59, 2008). The necessity of understanding the regulation processes of elements in the organisms demands determination of many elements in the organism, tissue, and cell (Baxter, Plant Biol., Vol. 12, 2009). A prospect for ionomics is environmental pollution where great variety of conditions and pollutants exist resulting in concentration and interelemental changes in the plant ionome. The capabilities of and problems with several multielement analytical techniques, including instrumental neutron activation analysis (INAA), X-ray fluorescence, inductively coupled plasma–atomic emission spectrometry (ICP-AES), inductively coupled plasma–mass spectrometry (ICP-MS), and atomic absorption spectrometry (AAS), which are adequate and most promising in ionomic and environmental studies of plants, are reviewed. References are confined mainly to the last 10–15 years. Information about concentrations, roles, binding forms, and pollution sources of the elements and comparison between methods with respect to limits of detection, determined elements, interferences, and economic considerations are tabulated. Some combinations of instrumental techniques supplementing each other are highly valued, namely, ICP-MS and ICP-AES and INAA and AAS or ICP-AES.     

A Review of the State of the Art,Limitations, and Perspectives of Infrared Spectroscopy for the Analysis of Wine Grapes,Must, and Grapevine Tissue

Abstract

As a fast and easy-to-operate technique, infrared (IR) spectroscopy has gained wide industrial acceptance for routine wine analysis. Considering the continuing improvements in hardware and software design and the analytical requirements of real-time or multiparametric analysis by the modern grape and wine industry, it is anticipated that in the near future IR spectroscopy will progressively become a routine method for process monitoring and process control in different stages of grape and wine production. This review highlights recent developments and applications of IR spectroscopy (near- and mid-infrared) to measure compositional parameters in wine grapes, grape juice, and grapevine tissues (e.g., leaves, stems, grapevine wood). In addition, some critical aspects and limitations in instrument availability, type of application, and overall understanding of the technology, which can be barriers for adoption of IR technologies by the grape and wine industry, will be discussed.     

15N, 13C-On-line Measurements with an Elemental Analyser (Carlo Erba,NA 1500), a Modified Trapping Box and a Gas Isotope Mass Spectrometer (Finnigan,MAT 251)

Abstract

An on-line method for the determination of ¹⁵N and ¹³C with a gas isotope mass spectrometer (Finnigan, MAT 251) was developed to improve the sensitivity and to reduce measurements time and the cost of the sample analysis. For this purpose an elemental analyser (Carlo Erba, NA 1500) was coupled to the mass spectrometer using parts of the capillary system of a trapping box (Finnigan, type CN). For the determination of samples with natural concentrations of ¹⁵N and ¹³C the uncertainty of the delta value is less than 0.2 δ‰. The detection limit is in the order of 10 μg (total N or total C) and 7 samples can be analysed per hour.     

Determination of essential elements (Mn,Fe, Cu and Zn) in herbal teas by TXRF,FAAS and ICP-OES

The aim of this study was the comparison of the results obtained in the determination of the content of essential elements such as Mn, Fe, Cu and Zn in vegetation samples using different analytical approaches, including suspension preparation and total reflection X-ray fluorescence ( TXRF) analysis as well as most commonly used spectroscopic methods in the field of vegetal analysis such as acid digestion in combination with atomic emission (AES) and atomic absorption spectrometry (AAS). In the case of TXRF analysis, two instruments equipped with different X-ray tubes anodes (W and Mo) were used to better evaluate the potential of TXRF for vegetal samples analysis. Analytical figures of merit for the considered methods were determined by the analysis of plant reference materials. The one-way analysis of variance (ANOVA) applied to the analysed and certified values showed that the results were not statistically different at the significance level of p-values <0.05. Therefore, suspension preparation and TXRF analysis proved to be a sustainable and fast analytical alternative to the most commonly used ones involving a previous digestion of the sample and inductively coupled plasma optical emission spectrometry (ICP-OES) or flame atomic absorption spectrometry (FAAS) analysis. Finally, the different analytical approaches were applied to the determination of Mn, Fe, Cu and Zn in a set of herbal teas used for medical purposes.     

SPECTROPHOTOMETRIC DETERMINATION OF ZINC IN PHARMACEUTICAL SAMPLES USING DI-2-PYRIDYL KETONE SALICYLOYLHYDRAZONE

ABSTRACT

A highly sensitive procedure for spectrophotometric determination of zinc has been developed. At pH 4.5, in 50% (V/V) ethanol-water medium and in the presence of di-2-pyridyl ketone salicyloylhydrazone (DPKSH), zinc forms a yellow complex which has maximum absorption at 376 nm The molar absorptivity is 4.82×10⁴ L mol^?1 cm^?1. The detection limit of this method is 62.1 nM for Zn(II).

The method has been applied to the spectrophotometric determination of zinc in pharmaceutical formulations and the results comply with those obtained by AAS. The proposed method is simple, rapid and accurate.     

The Hollow Cathode Discharge as a Spectrochemical Emission Source

Abstract

The hollow cathode discharge (HCD), a specialized type of glow discharge, has been the subject of investigations by physicists (in particular) and chemists for over a half century. Several hundred literature reports may be found concerning various aspects of the HCD. Despite this, many analytical chemists today would consider the HCD as merely a sharp line source for atomic absorption spectrometry (AAS). While this is certainly its most important present application, the HCD has a long history as a spectrochemical emission source allowing direct excitation and analysis of samples. Excellent sensitivities have been reported, but experimental difficulties, including construction of a demountable hollow cathode tube, have limited overall past acceptance of the HCD as an analytical emission technique. However, the current interest by analytical spectroscopists in new methods of atomization and excitation has revived interest in glow discharges. Also, the commercial availability of two demountable hollow cathode tubes and associated vacuum systems now allows easy accessibility to the technique.     

Calcination Effect on the Photoluminescence,Optical, Structural,and Magnetic Properties of Polyvinyl Alcohol Doped ZnFe2O4 Nanoparticles

Abstract

Spinel ferrite based nanoparticle material has been at the forefront of contemporary nanotechnology for use in various industrial and biomedical applications. The preparation and characterization of zinc ferrite nanoparticles (ZFNPs) doped with polyvinyl alcohol (PVA) are reported in this work. The formulated ZFNP/PVAs were characterized using powder X-ray diffraction (XRD), scanning electron microscopy (SEM), UV-visible spectroscopy, photoluminescence (PL) and a vibrating sample magnetometer (VSM). The XRD established the cubic spinel crystal structure of the as-prepared and calcined sample with an increase in the crystallite size after the calcination. The SEM analysis showed a spherical morphology within the range of 10-40?nm after calcination. The bandgap energy was enhanced after calcination. The PL analysis revealed a prominent peak in the UV band, which showed the characteristics of the formulated nanostructure. Transformation to a superparamagnetic nature was observed after calcination. It is noteworthy that after calcination of the formulated ZFNP/PVAs, the structural, optical, bandgap energy, morphology, photoluminescence and the magnetic properties were influenced and enhanced for various applications, chiefly for hyperthermia, magnetic resonance imaging, drug delivery and allied disciplines.     

Recent Applications of Fourier Transform Infrared Spectrophotometry in Herbal Medicine Analysis

Abstract

Fourier transform infrared spectroscopy (FTIR) is a fast and nondestructive analytical method. Associated with chemometrics, it is a powerful tool for the pharmaceutical industry. It is becoming a suitable technique for analysis of herbal medicine. This review focuses on the recent developments and updates for the qualitative and quantitative analysis of herbal medicine using FTIR. Moreover, it can be implemented during herbal drug development, in production for process monitoring, or in quality control laboratories.     

A REVIEW OF RECENT APPLICATIONS OF NEAR INFRARED SPECTROSCOPY,AND OF THE CHARACTERISTICS OF A NOVEL PbS CCD ARRAY-BASED NEAR-INFRARED SPECTROMETER

ABSTRACT

Near-infrared spectroscopy (NIRS) has been gaining popularity as an analytical tool due to advances in the power of personal computers, which allow the extraction of chemical and physical information about a sample, and the utilization of cost efficient and robust CCD array-based spectrometers. In this review, applications of NIRS are explored, within various fields of analytical chemistry, which take advantage of the inherent rapid analysis time and minimal sample preparation that is possible. For the purposes of illustration, the usefulness and limitations of a novel, PbS array-based spectrometer are described in the context of its application to the analysis of a variety of samples.     

Monitoring of extra-axial brain tumor response to radiotherapy using pseudo-continuous arterial spin labeling images: Preliminary results

IntroductionTechnological developments have increased the ease of performing perfusion MRI by arterial spin labeling (ASL) in clinical settings. The objective of this study was to evaluate the effects of radiotherapy on extra-axial brain tumors by using MR perfusion images obtained using the pseudo-continuous arterial spin labeling (pcASL) method.Materials and MethodsSix consecutive patients (nine lesions) with extra-axial brain tumors treated only with radiotherapy were enrolled in this study. MR examinations, including pcASL imaging, were performed before and after radiotherapy. Cerebral blood flow, maximum tumor blood flow (mTBF), tumor volume and the ratio of signal enhancement by contrast material (enhancement ratio) were evaluated in serial examinations during the course of radiotherapy. Both the percentage change in mTBF (mTBF ratio) and the percentage change in volume (volume ratio) were calculated using values obtained before and after radiotherapy. The correlation between the volume ratio and the mTBF ratio was assessed using linear regression analysis and Spearman’s rank correlation coefficient (r_s).ResultsA strong correlation was demonstrated between the tumor volume ratio and the mTBF ratio before and after radiotherapy (r_s= 0.93, P< .01). However, no significant correlation was identified between changes in enhancement and volume ratio (r_s= 0.20) or between changes in enhancement and mTBF ratio (r_s= 0.30) before and after radiotherapy.ConclusionThe mTBF measured using pcASL may serve as an additive index for tumor volume when determining tumor response to radiotherapy even in the absence of contrast material.     

A comparison study of inhomogeneous magnetization transfer (ihMT) and magnetization transfer (MT) in multiple sclerosis based on whole brain acquisition at 3.0 T

IntroductionMultiple sclerosis (MS) is a central nervous system disorder that may eventually affect its function. The clinical standard for MS severity is based on a clinical scale, which lacks lesion specific information. Magnetic resonance imaging of MS faces the challenge of myelin specificity, and in this work a new method inhomogeneous magnetization transfer (ihMT) is investigated as new biomarker of demyelination in MS.MethodsLocal ethics committee approved this study and written informed consents were obtained. Between Oct 2017 to May 2018, eighteen patients with relapsing-remitting MS (RRMS) (6 males, 12 females, mean age 31.2) and sixteen healthy volunteers (6 males, 10 females, mean age 30.4 years) were enrolled in this prospective study. All subjects underwent MRI exams including MT and ihMT imaging as well as the Expanded Disability Status Scale (EDSS) assessments. Independent sample t-test were used to compare the difference of ihMT parameters between healthy white matter (HWM) and normal appearing white matter (NAWM) and between HWM and MS lesions, respectively. Spearman correlation were used to analyze the correlation between ihMT parameters of MS lesions and EDSS score.ResultsThe ihMTR and qihMT demonstrate significant differences between WHM and NAWM groups, while no significant differences are observed for MTR and qMT. All parameters show significant differences between HWM and MS groups (p < 0.05). There was moderate negative correlation between MTR, qMT and EDSS score (−0.440 and −0.572), while there was a strong negative correlation between ihMTR and qihMT and EDSS score (−0.704 and −0.739).ConclusionBased on whole brain analysis at 3.0 T, ihMT showed better correlation with EDSS compared to magnetization transfer imaging, and may be a potentially valuable biomarker for demyelination in MS.     

Spectral,X-ray diffraction,surface morphological and thermal studies of gamma-irradiated potassium bis(oxalato)zincate(II)dihydrate

ABSTRACT

Potassium bis(oxalato)zincate(II)dihydrate was prepared and characterized. The sample was irradiated with ⁶⁰Co gamma rays up to 900?kGy. Infrared, Raman and photoluminescence spectra, X-ray diffraction pattern, surface morphology by AFM and SEM and non-isothermal decomposition of the complex were studied before and after irradiation. Spectral studies suggested significant radiation damage. X-ray diffraction studies showed reduction in unit cell volume and average crystallite size. Both unirradiated and irradiated samples of the complex belong to the hexagonal crystal system. Surface morphology of the complex changed upon irradiation. Thermal decomposition was enhanced.